Polyurethane of a polyisocyanate, an active hydrogen compound, and a hydroxyaryl aliphatic acid



United Stats atent Office 2,907,745 Patented Oct. 6, 1-959 2,907,745POLYURETHANE OF A POLYISOCYANATE, AN

ACTIVE HYDRGGEN CONIPOUND,ANB A HY- DROXYARYL ALIPHATIQ ACID 7 Claims.(Cl. 260.-47)' This invention relates to novel resinous compositions ofimatter of the polyurethane type and is directed more particularly tosynthetic resinous compositions derived from the reaction of hydroxyarylaliphatic acids with polyisoeyanates in: presence of am organicvcompound capable of entering: into the reaction and exerting aninfluence uponthenature of the resulting product- It is known: aurethane resin may be obtained by reacting a polyisccyanateor.polyisothiocyanate with a group of? compounds characterized by one ormore of what has; been termed: an active hydrogen: group. Foremostamong: the active hydrogen? compounds, at least as regards commercialdevelopment, have been the polyester compounds, although polyhyd'roxypoly-amino polya'rnidoa and polythio-c'ompounds are also recognized asbeing! more or less. useful in this connection. The resinous products:derived firom this reaction are d'epelrdent? for their characteristics,for the most part, upon the structure: of the activehydrogen: compoundwith the isocyanate: acting! principally as a physical coupling agentbetween: residues: of the polyester or other compound. The range orvariety ofi properties has thusbeen limited by the types or? structurespossessed: by available active hydrogen: compounds, andc the formulatorhas often found it quite diflicult to develop products having thedesired characteristics;

The primary object of the present invent-ion is the incorporation inapolyurethane-forming mixture of a compound having multiplefunctionality both with respect to: isocyanatesand isothiocyanates andactive hydrogen compounds, by means of which compound a' broad spectrumof polymers of this type can be obtained.

Another of the objects of this invention is to provide a new' class ofsynthetic resinous compositions which are capable of further reaction togive infusible; insoluble materials-suitable foruse as-protectivecoatings, adhesives, and molding resins having a variety of properties.

A further object is the synthesis along the general lines of establishedurethane reactions of a film-forming product characterized, by virtue ofthe novel reactants from which it is derived, with improved propertiesespecially as regardsresistance toattach by chemicals, resistance towear, and resistanceto penetration and solvent action by Water.

By suitable adjustment of the conditions of the reaction and the:ingredients, the product of'the invention may be caused to: assumeacellular or foam state, and; accord;

ingly, an additional aim ofthe invention: isthe provision of lightweightthree-dimensional solids possessing good structural strength and,therefore, useful in load bearing applications.

- These and other objects are accomplished by the present inventionwhich contemplates the reactioniof a substantial amount of an isocyanateor isothiocyanate, at least half of which: must contain? two or moreisocyanate or isothiocyanate groups per molecule, with an aliphaticacid, having. a total: of at least five carbon atoms with a singlecarbon. atom being substituted. with two hydroxyaryl groups, and anorganic compound having an active hydrogen groups at least two of thefollowing radicals: YH, (CYYH, NH and CYNHQ, whereY is oxygen orsultiurg. which compound is free of other reactive groups.

It. has been found that the addition of hydroxyaryl aliphatic acids to apolyisocyanate-active' hydrogen compound reaction mixture is anunusually advantageous measure for obtainingpol ymeric resinouscompositions characterized by excellent protective coating and adhesivepropert-ies' when used as a film, and high structural strength when.cast into: foam resin bodies. The hydroxyaryl aliphaticfacidsareespecially adapted for the reaction by virtue not only of the presenceineach molecule thereof ot a plurality of functional groups reactivewith both the: isocyanates and active hydrogen compounds, but because oithe novel combination of hydroxyland carboxyl radicals that make up thisplurality of groups. As will be explained more fully, both hydroxyl' andcarboxyl radicals condense with an isocyanatel group and; thus, are ofvalue in forming a resinous product; in addition, the carbonyl radicalduring the course of the condensation decomposes to liberatecarbondioxide which can be made use of in producing foam resin structures.Hyd'roxyaryl aliphatic acids are highmelting, cyclic compositions ofunique: symmetrical structure and. tend to contribute to the reactionproduct such properties as outstanding chemical resistance and superiorhardness and toughness. Chemical resistance is, for example, of greatvalue in the formulation of protective coatings which are likely to' besubjected in the course of ordinary usage to contact with variouschemicals. The presence in the resin of residues having a symmetricalstructure results in a more rigid product, afeature of much advantage inpolyurethane foams.

The hydroxyaryl aliphatic acids contemplated for re action according tothis invention may be, and preferably are, prepared by condensing aphenolic compound with a 'keto-acid under such conditions that twohydroxyaryl radicals are attached to the same carbon atomof the acid. Inorder for the yields of this reaction to achieve useful levels, itisnecessary, first, that the keto-carbon atom occur at the positionadjacent a terminal methyl group,

and; second, that the keto-acid has at least five carbons in acids thathave been found to be particularly suitable for use, as well as methodsof preparing the same. These acids consist of the condensation productsof levulinic acid and phenol, substituted phenols, or mixtures of phenoland substituted phenols and shall, for the sake of brevity, be referredto herein as the Diphenolic Acid. The term substituted phenols is usedherein to embrace phenols and phenolic compounds wherein one or morehydrogen atoms of the phenyl nucleus is replaced by an atom or groupthat does not enter into, or otherwise interfere with, the condensationof the compound with the keto-acid. Thus, for example, the nucleus maybe alkylated with a methyl or other alkyl group, preferably having notmore than five carbon atoms, as disclosed in the aforementionedapplication, Serial No. 489,300, or halogenated with bromine, fluorine,chlorine, or combinations thereof, provided that a total number ofsubstituents, including hydroxyl groups does not exceed three. TheDiphenolic Acid derived from substituted phenols, such as the alkylatedphenols, is sometimes more desirable than the products obtained fromunsubstituted phenols since the alkyl groups tend to provide betterorganic solvent solubility, flexibility, and water-resistance, as wellas influencing the nature and extent of subsequent reactions for whichthe acids are adapted. However, the unsubstituted product is usuallymore readily purified.

The second component necessary for the reaction of the present inventionis an isocyanate or isothiocyanate com pound. In order that a resinousproduct be obtained, the isocyanate or isothiocyanate compound mustcontain two or more isocyanate or isothiocyanate groups, a plurality offunctions being essential if a chain or cross-linked structure is to bedeveloped by condensation with the functional groups of the DiphenolicAcid and/or the active hydrogen compound. Accordingly, the isocyanatemay be defined as a compound having the general formula R(NCX),, where Xis a chalcogen having anatomic weight less than 33, i.e., oxygen orsulfur; z is an integer of more than one; and R is a polyvalent organicradical with the number of valences being equal to 1. There are numerouscompounds coming within this formula that are suitable for the reactionand no attempt will be made to give an exhaustive list. The followingare considered illustrative and will suggest to the expert a variety ofothers: alkylene diisocyanates; such as ethylene diisocyanate,trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylenediisocyanate, decamethylene diisocyanate, and their corresponding sulfuranalogues; cyclo-alkylene diisocyanate, such as cyclopentylenediisocyanate, cyclohexylene diisocyanate, and their corresponding sulfuranalogues; aromatic diisocyanates, such as mphenylene diisocyanate,naphthalene diisocyanate, di'

phenyl-4,4-diisocyanate, and their corresponding sulfur analogues;aliphatic-aromatic diisocyanates, such as xylene-1,4-diisocyanate,diphenylene methane diisocyanate and their corresponding sulfuranalogues; hetero-diisoand diisothiocyanates, such as SCNCH OCH NCS andSCNCH SCH NCS; and isocyanates and isothiocyanates having more than twoisocyanate or isothiocyanate groups, such as benzene1,2,4-triisocyanate, 1,2,2- triisocyanatobutane, and toluenetrisocyanate. From. among these and other polyisocyanates andpolyisothiocyanates, the following are preferred largely by reason oftheir ready commercial availability; toluene 2,4diisocyanate, toluene2,6diisocyanate, methylene bis(4-phenyl isocyanate), 3,3 bitolylene 4,4diisocyanate, and hexamethylene diisocyanate. In order to simplify theremainder of the discussion, the repetitious recital of both the oxygenand sulfur forms will be dispensed with; only the oxygen compound willbe given but will be understood as embracing the corresponding sulfuranalogue.

While, as has already been mentioned, urethane reaction requires apolyisocyanate compound, it is desirable for certain applications toalter the product by using, in addition, a minor portion of amonoisocyanate. Many of the reaction products of Diphenolic Acid withpolyisocyanates tend to be brittle infusible products; on the otherhand, this tendency may be counteracted by the addition to the reactionmixture of a proper amount and type of monoisocyanate, particularly whencombined with the proper amount and type of active hydrogen compound.Examples of suitable monoisocyanates are octadecylisocyanate, hexylisocyanate, and decylisocyanate, to mention just a few of the simplercompounds. Long-chain monoisocyanates, i.e. having more than 11 carbonatoms, are more effective as regards flexibility. Unsaturated compoundscan also be utilized and provide an additional curing or converting aid.The amount of the monocompound that is added to the reaction mixturewill vary depending upon the characteristics desired in the product. Asa general rule, there should be present a greater amount of thepoly-compound that the mono-compound, which is to say, that themonoisocyanate should be less than 50% of the total of all isocyanatesin the reaction mixture. If a more rigid, brittle material is sought,the quantity of the mono-form should be decreased, while, if moreflexibility is the desideratum, it should be increased toward the upperlimit just mentioned. The functional group of the mono-form may reactwith the carboxyl or phenolic hydroxyl groups of the acid to reducecross-linking within the polymer chain and thereby enhance the softnessand pliability of the polymer in proportion to the amount present, or afunctional group of each of two molecules of the monoisocyanate mayreact with two of the functional groups of a single molecule of acidand, thus, terminate the chain. Reaction of the mono-compound and theactive hydrogen compound is also a possibility, which reaction may alsoend the growth of the polymer molecule or reduce cross-linking.

The active hydrogen compound is the final component of the reactionmixture described herein. For the purpose of the invention, the activehydrogen compound must in clude at least two of the radicals OH, COOH,CONH NH SH, COSH, CSNI-I To simplify the discussion, compounds meetingthis requirement have been grouped into the following classes: (A) thepolyhydroxy compounds, (B) the polybasic acids, (C) the polyamines andpolyarnides, (D) miscellaneous analogous sulfur compounds, and (E) thepolyester resins. As will be seen later, compounds containing more thanone type of radical, i.e., hybrid compounds, have not been classifiedindependently but are included in these five groups. In this case, as arule, the compound is classified in that group of the several into whichit might fall by virtue of the radicals it contains, which has thehighest numerical designation in accordance with the above break-down.For example, a compound containing both hydroxy and amine radicalsappears with the sulfur compounds, and a compound having recurring esterlinkages and free carboxyl radicals appears with the polyesters.

The first of these classes are the polyhydroxy compounds, which, ascontemplated herein, embraces the aliphatic, alicyclic, heterocyclic,and aromatic compounds containing at least two hydroxy radicals.Examples of these compounds are the alkylene glycols, such as ethyleneglycol; polyalkylene glycols, such as diethylene glycol and theCarbowax" series manufactured and sold by the Carbide and CarbonChemical Company; glycerol, erythritols, higher alcohols, such asmannitol and soroitol; aromatic alcohols, such as resorcinol,hydroquinone, and bis-phenol; and resinous alcohols, such as theepoxides. Mixtures of the Diphenolic Acid with dihydric phenols,particularly the alkylidene diphenols, in reaction with the isocyanatesgive rigid, infusible products possessing excellent chemical resistanceto alkali and water when formed as films and outstanding rigidity whencast as some foamresin structures. It is well known that thepolyhydriealcohols, such as the long-chain glycols, given on reaction with theisocyanatessoft-flexi-ble-typecompositions of relatively low chemicalresistance. Modification of these compositions with D'phenolic. Acid hasbeen found to greatly increase the chemical resistance: of protectivecoating films prepared therefrom as well to strikingly heighten therigidity of: foam. resin structures produced therefrom.

Next in the classification are the polybasic acids. Ex-

amples. of these acids are the saturated al-iph-aticpolycarboxylic.acids such as adipic and tricarboxylic acid, azelaic acid; unsaturatedaliphatic-polycarboxylic acids, such as fumaric acid and aconitic acid,and aromatic polybasic acids, such as the isomers of benzenedicarboxylic acid. Polyfunctional acids are of particular interest inconnection with the formation of resin foams as the carboxyl groupdecomposes upon reaction with an isocyanate to release carbon dioxide.With the addition of a Diphenolic Acid, further carbon dioxideisavailable from the carboxyl group of the Diphenolic Acid and enhancedfoaming results. This is advantageous since enhanced foaming wasusuallypreviously obtained by adding substantial amounts of water. As is wellknown, water reacts with an. isocyanate to yield: carbon dioxide and acarbamide. Consequently, extensive foaming by the prior art methodrequired an excess? of isocyanate, a relatively expensive material,adding on a weight basis to the cost of the product and the reaction wasditiicult to control. In addition, the Diphenolic Acid serves tostrengthen the rigidity of-the foam and causes the cell arrangement tobe disconnected or closed rather than open. Where the combination ofisocyanate, polybasic acid and Diphenolic Acid is used as a film orcoating, the Diphenolic Acid tends to balance the essentially softinfluence of the polybasic-acid, permitting the formulation of tougher,harder films than would otherwise be the case. One interesting propertyof the polybasic acids in this association is their tendency to improvethe characteristics of the film in the. presence of water, presumablydue to the hydrophilic character of such acids. Films which are highlyhydrophobic. are. whitened by prolonged contact with water. By addingmaterial having hydrophilic properties to the film-forming mixture, thehydrophobic. character of the film can be: reduced to a level atwhichwhitening does not. occur without undue loss. of overall resistance towater.

The third class,.the polyarnines andpolyamides, is characterized by thepresence of an -NH radical, which in the ca se of the polyamidcs iscombined with a carbonyl.

group as the radical. -CONH Examples of this class are the alkylene andpolyalkylene diamines, such as ethylene diamine and hexamethylenediamine; heterocyclic polyamines, such as diethylene diarnine; andaromatic polyamines, such as phenylene diamine; the aliphatic diamides,such as malonamide, succinamide and adipamide; aromatic diamides, suchas phthaldiarnide; and the: resinous polyamides; groups. are ofparticular value in accelerating the reaction. It. isinteresting toobserve that polyamines are slightly more inclined to impart:flexibilityto products than the polyamides. Thus, a product of balancedflexibilityrigidity, or increased. rigidity, may be obtained by theaddition of a Diphenolic Acid. The poly-nitrogen compounds are alsouseful where products havinghigh chemical and water resistance aresought.

Another class of active hydrogen compounds is thesulfur-containingchemicals. As a general rule, this class embraces thecorresponding sulfur analogues of the members of the other classes.Thus, polythiols, such as ethanedithiol and propane-trithiol,polythioacids, polythioamides, and resinous polythio-compou-nds areincluded among others. in The most useful of these compounds are thethioresins sold under the trade name Compounds containing aminolustratcd as follows:

fide with anorganic dihalide, trihal'ide, or mixtures of the two. Thesepolymers. are thought to have thiol terminal groups. Preferably, theliquid polymers are employed because of. their relatively low molecularweight, ease in handling, and ease in admixing with other reactants. Asis well known, these materials undergo reaction with various couplingagentsor can be cured with numerous curing agents to form rubberypolymers which are usually soft and flexible. When compounded with aDiphenolic Acid and an isocyanate, thioresins yield smooth, tough,flexible productshaving much augmented chemical resistance. Other sulfurcompounds, such as the simple mercapto acids andmonoanddi-mercaptans,may be used in conjunction with Diphenol'ic Acid in the formulation ofvaluable coating, adhesive, and molded objects.

Finally, there are the polyester resins, which are polymers, havingrecurring ester linkages and unreacted hydroxyl and carboxyl' terminalgroups formed by reacting a polyb'asic acid with apolyhydric alcohol.The nature of the reactive groups is determined by the proportion of thereactants. Thus, an excess of the alcohol favors terminal hydroxylgroups while an excess of acid favors terminal carboxyl groups. Byproperly balancing the amounts of each, terminal groups of both kindscan be procured. There are a number of polyester compounds availablecommercially, one example being a series having hydroxyl values withinthe range of 7 0-1000 and acid numbers Within the range of 0-80 soldunder the trade name M'ultron by the Mobay Chemical Company. Among thepolybasic acids that can be used are succinic, adipic, maleic, sebacic,azelaic, fum-aric, and dimerized acids, such as dimerized vegetable oilacids prepared and soldby Emery Industries, Inc. Suitable polyhydricalcohols include ethylene glyeol, diethylene glycol, triethylene glycol,pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol,mannitol, glycerin'e, trimethanol propane and triethanol propane.

It is well known that reaction of polyester resins with thepolyisocyanates results in soft flexible foam resin structures and softcoating compositions and molding materials. The use of Diphenolic Acidinconjunction with these polyesters and isocyanates has been found to bean excellent mode of promoting rigidity in: foam resin. structures ofthis type. Thus, moderately to completely stilf three-dimensionalarticles. can be easily obtained merely by incorporation of the acid inselectively increased amounts. Variation in density of the solid productmay also be effected by this means. In the field of protective coatingsand adhesives, an analogous hardening and toughening influence by theDiphenolic Acid exists so that products of this kind displaysubstantially enhanced resistance to chemical attack and deteriorationas well as general wear and tear Without necessarily involving unduesacrifice of the natural flexibility and clarity of the polyesterresins.

The general chemistry of the present reaction is basi cally simple. Itis well known that isocyanates react with the various chemicalfunctional groups. of the compounds employcd herein and these reactionsmay be il- (1) Hydroxyl group:

ROH-f-R'NCOeRNHCOOR (2) Carboxyl group: RCOOH-l-RNCO-aRNHCOOCOR-RNHCOR+CO (3) Primary amino group:

RNH +RfNCO- RNHC0NHR. (4) Amido group:

RCONH -I-RNCO RNHCONHCOR The same. reactions take placewhere sulfur issubstitutedg for any oxygen in these reactants.

In the present invention, it is postulated that the reaction occurswithin a system of three or more components, each of which ischaracterized by at least double functionality. Accordingly, while theunion of any two groups will proceed as set forth above, it will beappreciated that the resultant product will in any case be polymeric.Further, it will be apparent that the possible arrangements that may betaken Within the polymer molecule by the residues of the reactants areentirely too numerous to be presented herein. Due to the high reactivityof isocyanate groups, one would expect the condensation between thesegroups and the functional groups of the Diphenolic Acid to takeprecedence over any possible reaction between the acid and the activehydrogen compound. Thus, it can be predicted that the polymer moleculecomprises Diphenolic Acid residues linked together by isocyanateresidues alone or which are themselves coupled by means of the residuesof the active hydrogen compound. Where the isocyanate and activehydrogen compound are difunctional, the acid residues would be separatedby essentially linear chains with cross-linking taking place between theresidues in adjacent chains due to the three reactive groups of theDiphenolic Acid. With isocyanates and/or active hydrogen compoundshaving more than two functions, crosslinking to a much greater degreewould ensue.

The diversity of the isocyanates and active hydrogen compounds that canbe employed makes it virtually impossible to prescribe a fixed set ofrules governing the choice of a class of compounds, the particularmember of that class, as well as the amounts of the member. Some of theclasses and the 12 individual members are more or less equally suitedfor use in producing a given product so that a choice depends in manyinstances upon the personal preference of the formulator, suchpreference being based, for example, on his greater experience inworking with certain types of materials than with oth ers. As a rule,aliphathic compounds favor flexibility and softness with the extent ofthese properties increasing with the chain length. Conversely, compoundshaving a tightly knit or cyclic molecular structure favor rigidity andhardness. As a consequence, a wide range of properties can be developedby the careful selection of reactants: that is, all may promoteflexibility, they all may promote rigidity, or some one and some theother in order to cover the gamut. between the two extremes.

Along with the specific reactants, the properties of the product arealso influenced by the amount of each reactant that is employed. Becauseof the high reactivity of the isocyanate, for the purpose of definingproportions it may be considered that the Diphenolic Acid and activehydrogen-containing compound react as a unit with the isocyanate. Withinthis suppositious unit, the active compound may constitute from about toabout 65% of the whole, determined on the basis of equivalent weight,with the acid making up the rest. Below 5%, the effects of the activecompound are rarely significant, while above 65%, the contribution ofthe acid is counteracted excessively or is not sufficiently great to beof real value. Experience has indicated that the Diphenolic Acid andactive hydrogen compound, considered together, may be reacted inamounts, again calculated on an equivalent basis, varying from aboutonefifth of the isocyanate up to about five times the isocyanate. Someproducts prepared from amounts outside this range may display usefulcharacteristics attributable to all three of the reactants, but thisappears to be the exception rather than the rule, and, for the mostpart, valuable products fall within this range. From a consideration ofthe reaction, it will be appreciated that the optimum situation prevailswhere all of the functional groups of the acid and active hydrogencompound are 8 reacted with functional groups of the polyisocyanate. Forthis reason, a preferred range is 2:1 to 1:2. of acid and activecompound to isocyanate onan equivalent basis with a '1:1 ratio beingmost desired. 1

If a monoisocyanate is employed along with the polyisocyanate, thenumber of reactive foci of the Diphenolic Acid and active hydrogencompound available to the functional groups of the polyisocyanate islessened. In arriving at the amounts of reactants to be utilized, themono-compound must therefore be considered, and in such case theequivalent weight of the isocyanate is the total of the equivalentweights of the monoand polycompounds.

In general, the procedure by which protective coating films are preparedin accordance with the present invention involves merely adding atordinary temperatures the Diphenolic Acid and active compound to theisocyanate, forming a film of the desired thickness of the mixture, andconverting the mixture by exposure either. to air at normaltemperatureor to heat. In some cases, it is desirable to dilute some or all of thereactants, e.g., in order to lower the viscosity of the mixture and,thus, vary the film thickness of a single coat, and/or in order todissolve the Diphenolic Acid at room temperature. Any solvent that isinert to both the acid and isocyanate may be used, an example beingmethyl ethyl ketone among many others. The mixture of reactants, eitherdiluted or not, has been found to be reasonably stable provided it isnot heated or exposed to air for excessive periods. Such stability is afeature of considerable importance as it permits large quantities of themixture to be made up at one time and then used as needed. For heatcure, temperatures of about 175 C. for times of about one hour to aboutfive minutes have been found satisfactory. For a room temperature cure,it is preferred thatany of the well known conversion catalysts forreactions of this type, such as triethanolamine, be added in smaliamounts in order to reduce the amount of time needed for the film toharden. When early conversion is of no special advantage, the catalystmay be dispensed with; As the examples show, the characteristics of thecured films vary with the particular combinationof reactant and amountsthat are employed, with some being better than others, as wouldordinarily be expected. As a whole, however, the films possesscharacteristics that compare favorably with many other availablematerials so that the product of the invention is quite useful for avariety of purposes. For example, in numerous instances, the filmsoftthis invention have withstood boiling water for 16 hours and a 5%caustic solution for more than hours without any indication of failure.

Where solid foam or cellular structures are desired, they may beobtained by mixing the concentrated Diphenolic Acid and active hydrogencompound with a suitable conversion catalyst, of which triethanolamineis again an example, in an appropriate reaction vessel at temperaturesat or above the melting point of the acid, adding the isocyanate whileagitating, pouring the mixture into a mold, allowing the mixture to foamunimpeded, and converting by heating, as in a draft oven, at atemperature of about 80-l75 C. or more for from about 5-30 minutes, orby normal temperatures for much longer periods of time. Although notessential, it is usually desirable to employ an emulsifier in order toob tain a more homogeneous mixture of the reactants. The' reactionusually proceeds instantaneously at or above the melting point of theacid. The instant process may be carried out readily in any system whichprovides for stirring and has sufficient space for the foaming action toproceed unhindered. A modification of a unit cI.11.'

fently used in commercial urethane foam production may be employed. Sucha system comprises two supply tanks connected to a pressure-mixingnozzle by suitable feed lines. One tank contains the isocyanate and theother tank contains the Diphenolic Acid and active compound emulsifiedwith the emulsifying agent and catalyst. As pure or substantially pureDiphenolic Acid is solid at room temperatures the latter tank must beheated. The acid and isocyanate, are fed from the tanks to the nozzlewhere they are mixed under pressure and flowed into pans where thefoaming reaction is allowed to proceed unhindered. Again, the foams maybe cured in a suitable draft oven at elevated temperatures, thusaccelerating the operation. Although the foams may be cured at ordinarytemperatures as in the case of the films, this considerably prolongs thecuring time and a heat cure is preferred.

As has already been briefly mentioned, the Diphenolic Acid as well ascarboxyl-containing active compounds are especially well suited for theformation of urethane foams by reason of the carboxyl group or groupswhich they contain. These groups in the course of the reaction decomposeto form gaseous carbon dioxide which bubbles through the mixture toproduce a cellular-structure. Thus, a foaming medium is inherentlypresent, eliminating the need, in many instances, of an external foamingagent, this being especially true where a polybasic acid constitutes theactive compound. With other active compounds the use of external foamingagents, such as Water, to assist in the foaming action may not be precluded entirely as it sometimes proves advantageous to add small amountsof water, say up to about by weight of the mixture. The use of watermerely as an assistant does not add unduly to the curing time of onehour or less which is in distinst contrast to typical present commercialpolyurethane foam processes, wherein water is relied upon as the sole orprincipal foaming agent, which require a post-cure of some 24 hoursduration. The density of the foams made as described herein varies notonly with the particular isocyanate selected for reaction but with thetemperature of the conversion as well. It has been found that as thetemperature of this stage is increased, the density of the foam alsoincreases, due presumably to the increased loss of CO from the mixtureat the higher temperatures.

The toughness and rigidity contributed by the Diphenolic Acid areespecially significant in the case of foam structures made in the pastfrom isocyanate and active hydrogen compound reaction products whichhave, for the most part, been of 'rather soft, spongy texture. Thetoughness and rigidity together with the resistance to Water and commonchemicals that the present foams exhibit as well as a very low densitywhen compounded to this end, constitute a rather exceptional combinationin this field, so that the present invention should be particularlyvaluable in producing foam structures for such uses as air domes,insulation, crash linings for vehicles, aircraft, etc., and structuralcomponents alone or in conjunction with outer coverings of wood ormetal.

-For the sake of brevity as well as convenience, most of the remainderof this disclosure will be presented in the form of four tables, thefirst three giving examples of the three reaction components, along withsome pertinent information concerning them, and the fourth providingworking examples of the invention in the coating field.

It will be observed that an isocyanate equivalent is specified for eachacid. The isocyanate equivalent is defined as the weight of the acidwhich will react with one equivalent of the isocyanate and will be ofassistance equivalent is specified for each isocyanate.

Isocyanate equivalent (observed) Abbre- A cid viation Condensationproducts of levulinic acid and phenol: A mixture consisting of 376 partsof phenol, 116 arts of levulinic acid, and 250 parts of 37 0 aqueoushydrochloric acid was agitated at 4852 O. for 66 hours. The upperorganic layer was removed from the aqueous H01 for decantation. Theproduct was then purified by vacuum distillation of the volatileunreacted materials by heating to 180 C. at 32 mm; pressure. Theresidual product amounted to 247 parts (86.5% of theoretical) having asoftening point of C. and an acid numbar of 155. Purification of thisproduct by first dissolving in aqueous bicarbonate solution,reprecipitating with mineral acid, followed by recrystallization fromhot water gives a white crystalline compound melting at 171l72 0.,having an acid value of 196.

Condensation product of levulinic acid and meta-cresol: A mixture of 378parts (3.5 mols) oi metacresol, 116 parts (1 mol) of levuliuic acid, and250 parts of 37% aqueous hydrochloric acid was agitated at 50 O. for 72hours. The upper organic layer was removed from the aqueous E01 bydecantation. The product was then pur1- fied by vacuum distillation ofthe volatile unreacted materials by heating to 170 C. at 30 mm.pressure. The residual product has an acid number of 166 (theoreticalfor the pure Diphenolic Acid=178). The yield amounted to 184 parts(58.6% of theoretical).

Condensation of levulinic acid and a mixture of phenol and ortho-cresol:Similar treatment of a mixture of 3.5 inols of a technical cresolcontaining 40 parts phenol and 60 parts ortho-cresol, 1 mol of lcvulinicacid, and 250 parts of 37% hydrochloric acid gave 275 parts (90.5% oftheoretical) of a product having and acid number of 149.

Condensation of lcvulinic acid and xylenol: Similar treatment of amixture of 3.5 mols of technical xylenol, a crcsylic acid, supplied bythe Koppers Company, Inc, under the trade name X-2, which containsxylenols of which about 30% is 3,5- xylenol and has a distillation rangeat the 5% point of 214-217 C; and at the 95% point of 220-225 0.; 1 mollevulinic acid; and 250 parts of 37% hydrochloric acid reacted at 50 C.for 96 hours gave a prod not having an acid number of 166 in yields ofaround 50% of the theorctical amount.

DPA 89. 7

DCA 19s DPCA 235 DXA 168 in selecting actual amounts of the acid thatshould be used. The method used in determining the observed values aslisted involves reacting a sample of theacid with an excess oftoluene-2,4-diisocyanate and then determining the excess isocyanate byreaction with di-n-butylamine. Specifically, the technique used is asfollows:

To 25 ml.,of methyl isobutylketone is added 3 grams oftoluene-2,4-diisocyanate previously standardized against di-n-butylamineand a weight of the acid such that the diisocyanate is present inapproximately excess. To this mixture is added triethylamine in. anamount equal to 1% The mixture is refluxed for a period of one hour.After cooling to room temperature, the condenser walls are rinsed withabout 25 ml. of redistilled toluene. To this mixture is added 25 ml. of2 N di-n-butylamine. This mixture is warmed to the boiling point,allowed to stand for one hour at which point 75 ml. of methanol isadded, and the excess di-n-butylarnine back-titrated with 1 N alcoholichydrochloric acid.

The acid number given for each acid has its usual meaning, which is thenumber of milligrams of potassium hydroxide necessary to neutralize theacid. content of one gram of the sample, and provides an indication ofthe degree of acidity of the product.

It will be noted that an observed and theoretical amine The amineequivalent refers to the weight of the isocyanate containing oneisocyanate group of the weight of isocyanate and the acid.

and reacting with one molecarefully cleaned and dried 250 ml. or 500 ml.Erlen-' meyer flask. sample of diisocyanate was drawn TABLEII.REPRESENTAT[V E ISOCYANATES Amine equivalent No Commercial source,trade name, and abbreviation Structure Observed Theory 1-. E. I. du Pontde Nemours & 00., 1110.; 'Hylene '1; N00 90. 62 87.07

Toluene-2,4-diis0cyanate E. r. du Pont de Nemours & 00., Inc.; Hylene M;OCN-CNCO 139.98 125.12

Hy M. l

Methylene bis(4-phenyl isoeyanate) Bile 7 Me 3. National Aniline Div.;Naeeonate 200; N 200 O CN NC 0 132, 7 132, 13

3,3-bitolylene-4,4-diisocyanate 4.. Mobay Chemical 00.; Mondur N5; M0 N5l 116. 58 105-0 l O O N N aphthylene-1,5-diisocyanate l 5 Mobay Chemical00.; Mondur TM; MO TM 0H3 0-H 107. 78 123. 45

--NC O I OH;

Triphenylmethane triisocyanate 6 Mobay Chemical 00.; Mondur HX; MO HXO0N (0H2)0N00 103. 39 84.01

Hexemethylene diisoeyanate 7 Mobay Chemical 00.; Mondur 0; M 0Ha(0H2)nNCO 342.32 295.0

Oetadecylisocyanate C|JH CH 8 Shell Development 00.; Durenediisocyanate;Dur.-. 0 ON NC 0 111.22 108. 12

l CH3 CH3 2,3,5,G-tetramethyI-I,4-benzene diisoeyanate technicalmethanol and 0.5 ml. of bromophenol blue in-' dicator was added. It wasthen titrated with 1 N HCl to a yellow end point. The indicator wasprepared by taking 0.1 g. of bromophenol blue, 1.5 ml. of 0.1 N-

NaOI-I diluted with. 100 ml. of distilled H O. The average precisiondemonstrated by these determinations was TABLE III.- ACTIVE HYDROGENCOMPOUNDS A. POLYZEIYDROXY COMPOUNDS Isocyanate equivalent TheoreticalEthylene glycol 1,4-butanedio1 Diethylene glycol. Polyethylene glycol400 (Carbide & Carbon Chemicals stokes at 210 F.)

Polyethylene glycol 1000 (Carbide & Carbon Chemicals Polyethylene glycol4000 (Carbide 8: Carbon Chemi Polyethylene glycol 6000.

Glycerol (C.P. grade). Pentagryt hritol with bis(4-hydroxyphenyl)-dimethyl oint (Durrans Mercury Method, .T 1929]) of 40-450.; epoxide equivalent 300-375.) Epon 1007 .1 (Shell Chemical Corp. Auepoxy r with bis(4-hydroxyphenyl)-dime point (Durrans Mercury Method) of127-133 0.; e Bis (4-hydroxyphenyl)-dimethyl methaneformaldeh (In a 3liter, 3-neck flask provided with a mechanic condenser was placed 912parts of bis(4-hydrox 37% aqueous formaldehyde and 2.3 parts oxalic amixture was heated to reflux temperature and tillation at reducedpressure using a water aspirat 30-40 mm. The flask temp. during theremoval 7090 C. The product, amountin The nonvolatile content was 83.4%.p-t-Butylphenol-formaldehyde condensate (The procedure of preparationincluding the deh with bis(4-hydroxyphenyD-dimethyl m tertiarybutylphenol, 1,067 parts of 37% aqueous formald hydroxide was used togive a final product. The nonvolatile content was 93.6%.)

Resorcinol Hydroquinone; 6:1 :11:

1,5-dihydroxynaphthalcna...

4,4dihydroxybenzophcnone Bis(4 hydroxyphenyl)-dimethy1 methanendensationof e iifiiiiiiifi' ence of alkali hav Colour Chemists Ass 11 eoxy resin prepared from the co methane in the pres densation ofepichlorohydrin nce of alkali havin poxide equivalent 1,550

esin prepared from th thyl methane in the prese a1 agitator, athermometer, and a reflux ylJ-dimethyl methane, 960 parts of ithcontinuous agitation the re action ng continued for 1 hr. After permitofthis last portion of water ranged from ts, was a clear, heavy, syrupymaterial.

ethane above. A mixture of 1,000 parts of paraa, more, 750

B. POLYBASIO ACIDS Azelaic acid Adipic acid:

Aconitic acid.

Diglycolic acid- Isophthalio acid Oomcnm IO sw p s? QOOOOH OMKOOWNH O.POLYAMINES AND POLYAMIDES Hexamethylenediamine Diethylenetriamine- II:

Tricthylene tetraamine.

Phenylene diamine i Diethanolamiue Adipamide Phthalamide. Malonamidep-Toluenesrflionamide- Polyamide resin i (In a 3-liter 3-neck flashprovided with mechanical agitator, with a reflux condenser above wasplaced 1,545 parts ofE Acid #955 (a dimerized soya bean oil acid) and269 parts was provided with an inlet for an inert gas. With contatmosphere of nitrogen gas the reaction mixture was he of 12 hours. 165parts of Water were removed from the r The resulting polyamide resin hadan acid number of 3.

(Durrans Mercury Method).)

thermometer, an mery Industries, Inc., Dimer of ethylenediamine. Theflask inuous agitation and in an inert ated from 94-220" C. over aperiod eaction mixture during this period. 2, and a softening point of8789 C.

D. SULFUR-CONTAINING COMPOUNDS Thiomalic acid i Thioglycolic acidThiourea Z-mercaptoethanol Thiokol Liquid Polymer LP3 .1

,200 centipoises.)

having viscosity at 25 C. of 700-1 Thiokol Liquid Polymer LP-S ((ThiokolChemical Corp.) Described as having 0 E CH2CH2-OCH2-Q having viscosityat 27 C. of 250350 centipoises.) Thiolrol Liquid Polymer LP-33 ((ThiokolChemical Corp.) Described as having formula S(O2II4 O 'GH2O G2H havingviscosity at 25 C. at 1,300-1,550 ce 1 Preparation of these epoxidematerials as well as illustrative examples are described in U.S. Patents2,456,408, 2,603,726, 2,615,007,

2,615,008, 2,688,805, 2,688,807, and 2,698,315.

Abbrev. Isoeyanate equivalent Compound used in tables ObservedTheoretical Polyester resin 2 PER 1..-. 246.1 (A succinlc acid, azelaicacid, ethylene glycol, and glycerol polyester.) Polyester resin 3 PER2.... 107. 4 (A glycerol, azelaic acid and succinic anhydridepolyester.) Polyester resin 4 PER 3...- 929.0 (A diethylene glycol,adipic acid and glycerol polyester.) Polyester resin 5 PER 4.-.- 480.5(A diethylene glycol and adipic acid polyester.) Polyester resin PER5.-.. 1,046 (A diethylene glycol and phthalic anhydride polyester.)

2 In a 3-neck flask provided with a thermometer, a condenser attachedthrough a water trap, and a mechanical stirrer was placed 502 partssuccinic anhydride, 943 parts 204 0. with continuous agitation at whichpoint a sufficient amount of xylene was added to give constant refluxingat After refluxing for 2 hours at l95-204 0., 462 parts of glycerol wasa was continued for 2 hours and minutes at 204-220 O. at which po syrupyproduct had a nonvolatile content of 96.5% and an acid value of 6.

a As in the preparation of PER 1, 925 parts of glycerol, 785 parts azwith xylene at l84-204 O. for 3% hours. Most of the xylene was removehad a non-volatile content of 95% and acid value of 7.6.

4 As in the preparation of PER 1, 212 parts of diethylene glycol, 2 withxylene at 200-225 G. for 6 hours. 80 mm. The viscous syrupy product hadan acid value of 12.8.

5 As in the preparation of PER l, 212 parts of diethylene gly 225 0. for6 hours. The xylene was removed by heating at 200-225 syrupy product hadan acid value of 87.

As in the preparation of PER l, 212 parts diethylene glycol and at200225 C. for 6 hours. The xylene was removed byEheating at 220-2viscous syrupy product had an acid value of 60.

The following examples, presented in tabular form to conserve space,illustrate the conversion of mixtures of polybasic acids andpolyisocyanates alone and modified with a monoisocyanate to insoluble,infusible products. Each of the resinous acids was dissolved in thedesignated solvent to a non-volatile content of -60%.

25 C. with reduced pressure of around -80 mm.

elaic acid, and 418 parts of succinic anhydride were refluxed d bydistillation at 200-205 C. The viscous syrupy product 92 p The xylenewas removed by heating col and 292 parts of adipic acid were refluxedwith xylene at 200- C. with reduced pressure of around 70-80 mm. Theviscous arts of adipic acid, and 2 parts of glycerol were refluxed at220225 O. with reduced pressure of around 70- 5 parts of phthalicanhydride were refluxed with xylene The however, the modifier wasdissolved in small amounts of the same solvent for solubility purposes.The mixtures thus obtained were applied to glass panels at 0.002" wet.

film thickness. The table gives the heat treatment used for conversionand indication of film flexibility and wah isocyanatgs and d fi wereused in most exam. ter and alkali resistance in actual applications. Allparts ples at 100% non-volatile content. In some instances, are byweight.

TABLE IV.EXAMPLES OF THE INVENTION AS A COATING A. POLYHYDROXY COMPOUNDConversion Withfirood in S. Tri- Film Ex. No. D phe; Parts Isocya-'Parts ethyl- Active Parts Solvent propernolic acid nate amine, compoundties H20 5% aq. parts Time Temp, at N aGH (hrs.) 0. 100 0. at

89. 7 39. 3 0. 5 175 F1exib1e-- 16+ 50+ 89.7 44. s o. 5 175 do-..-.-.16+ 50+ 89. 7 32. 7 0. 5 175 Brittle. 8 89. 7 27. 6 0. 5 175 Flexible..16+ 25 89. 7 29. 5 0. 5 175 Brittle- 16+ 134. 6 204. 9 0. 5 176Flexible.- 2 08 80.7 HY T... 181 1311011864.. 155.8 0.5 175 Brittle---16+ 89.7 HY T... 181 BDF 49.4 0.5 .08 89.7 HY T-.. 181 R 105.4 0.5 .2589.7 HY T.-. 181 221 0.5 .08 44.8 HY T.-. 127 273.8 0.5 175 -.-(10... 27 89.7 HY M.-. 280 39.3 0.5 175 Flexib1e-- 16+ 50+ 107.6 lIY M... 28031.4 0.5 175 Brittle-.- 16- 50+ 71.8 HY M... 280 53.7 0.5 175 F1exible..16- 90+ 107.6 HY l 280 130. 8 0. 5 16-- 90+ 71.8 HY M... 280 33.2 0.516- 50+ 89.7 HY M... 280 29.5 0.5 16- 50+ 44.8 HY M... 154 14.5 0.5 16-90+ 107.6 HY M... 280 144.1 0.5 16-- 90+ 44.8 HY M... 238 66.1 0.5 l6.75 89.7 HY M... 280 114 0.5 16- 90+ 89.7 MO HX. 207 39.3 0.5 16-- 50+107.6 MO HX. 155 13.4 0.5 12-- 6 152.5 MO HX. 207 8.3 0.5 16- 50+ 89.7MO HX. 207 29.5 0.5 16- 28 89.7 MO HX. 207 24.2 0.5 16-- 90+ 89.7 MO HX.207 155.8 0.5 16- 90+ 107.4 MO HX. 196 34.5 0.5 16-- 7 53.8 MO HX. 15549.5 0.5 ...(10 16-- 90+ 71.8 MO HX. 186 186.1 0. 5 175 Brittle--. 4 .0889.7 MO HX. 186 91.2 0.5 175 Flexible-- 8 8.5 89.7 N 200.... 266 39.30.5 175 ...(10 16- .08 89. 7 N 200.... 266 44. 8 O. 5 175 Brittle..- 16-.25 161. 5 N 200--.. 266 32. 7 0.5 175 16- .75 XXXV.-.- DPA-..-. 44.8 N200.-.. 266 41- 5 0.5 175 16+ .25

TABLE IVQ-EXAMPLE OF THE INVENTION AS A COATINGContinued I).SULFUR-CONTAINING COMPOUNDS Conversion Withstood in hrs. Tri- "i FilmEx. N0. Diphe- Parts Isocya- Parts ethyl- Active Parts Solventpropernolic acid nate amine, compound tles H20 5% aq. parts Time Temp.,at NaCH (hrs) 0. 100 0. at

17.9 40. 6 MIK/DMSO 0. 5 175 Brittle- 08 08 9.0 418 MIK 1. O 200Flexible- 08 .08 44. 9 17 MIK/DMSO 0. 5 175 Brittle. 16+ 96+ 9, 3. 6MIK/DMSO 0. 175 Flexible 16+ 96+ 44.9 1.5 MIK/DMSO 0.5 do -.08 179. 478. 1 MIK 0. 5 Brittle-- 1 259.4 1.9 Dioxane/DMSO 0.5 do -.08

84 76. 1 Dioxane/MIK 0. 5 1 165. 1 59. 8 Dioxane/MIK. 1.0 .25

99. 2 1. 5 Dioxane 0. 5 3 99. 2 114. 2 Dioxane/MIK 0. 5 1

E. POLYESTER RESINS 73 0. 5 175 Flexible" 32 73 0.5 175 0 15+ 2 73 0.6175 do 15+ 2 73 O. 5 08 73 O. 5 75 146 0. 5 80+ 219 0. 5 80+ 48 0. 5 01648 e 0. 5 .25 48 0. 5 .02 73 Y 0. 5 7 43 0. 5 5 93 0. 5 32+ 31 0. 5 23219 O. 5 175 Flex 23+ 55+ 146 0. 5 175 do 23+ 55+ 73 0. 5 175 Brittle.15+ 8 98 0. 5 6. 5 98 0. 5 55+ 73 0. 5 0B 73 0. 5 08 52 0. 5 8 62 O. 5 862 O. 5 8 37 0.5 120+ 47 0. 5 120+ 31 0. 5 1 37 0. 5 120+ 24 0. 5 25 520. 5 48+ 47 0. 5 8 08 31 0.5 175 d0- 16+ 120+ PER 2.--- 62 Dioxane 0. 5175 Flexible. 16+ 120+ It will be understood that the description offlexibility is purely relative and indicates merely whether or not asubstantial part of the film could be peeled or stripped intact from thepanel. Varying degrees of flexib-ilityor brittleness areencompassed bythe general descriptive terms used. Products which might 'be too brittlefor I use on film wherein considerable flexibility was a requisite wouldnevertheless be useful in films where flexibility is of no importance orin'cast or molded articles.

In order to demonstrate the preparation of a foam resin structure inaccordance with the invention, the following examples were prepared:

, Example CLX V 44.9 parts DPA, 15 parts water, 27 parts ofpolyoxyethylene sorbitan mono-oleate, an emulsifier sold under thetrade-name Tween 80 by Atlas Powder Company, and 1.8 parts oftriethylamine were stirred with 369 parts of the polyester resin that isdesignated PER 1 in Table 3 in an open container until a homogeneousmixture was obtained. 299 parts of toluene-2,4-diisocyanate f wereadded, with continuous stirring, and the mixture allowed to foam freely.The temperature of the mixture was maintained at 25 C. until the producthad solidified. The result was a rigid foam which was relativelyunbrittle. r r Eixlalmple CLXVI Example CLXV was repeated, employing22.5 parts DPA, 14 parts water, 25 parts Tween 80, 1.8 partstriethylamine, 369 parts of polyester resin PER 1, and 272 parts toluene2,4-diisocyanate. The conversion was also carried out at 25 C. Theproduct was similar to that of Example CLXV inthat the foam Was rigidbut relatively unbrittle. I Example CLX VII Example CLXV was repeated,except that 181 parts of toluene 2,4-diisocyanate, 9 parts of water, and464 parts of the polyester resin designated PER 3 in Table 3 wereemployed. Again, the mixture was converted at 25 C. The foam that wasproduced was flexible with relatively low rigidity.

In the preceding three examples relating to foam products, the polyesterresin was at liquid at ordinary temperature and was mixed with the DPAby melting the latter and stirring. After cooling to room temperatures,the mixture remained sufficiently fluid to be easily mixed with theisocyanate. Where the mixture of DPA and active hydrogen compound is notsuffieientlyfluid at room temperature, it may be heated to its meltingpoint and the reaction allowed to proceed upon the addition of theisocyanate. It is preferred that the foaming be allowed to take place atthe lowest possible temperature consistent with proper mixing since hightemperatures appear to promote non-uniform cell structure.

The aforegoing examples are furnishedonly for the guidance of thoseseeking to practice the invention and not for the purpose'of definingthe boundaries within which it is operative. Numerous other embodiments21 are possible and will be suggested by these few illustrations.

Having thus described the invention, that which is claimed is:

1. A composition of matter comprising the polymeric reaction product of'(A) a compound of the general formula R(NCX) wherein R is an organicradical having a valency equal to z, X is a chalcogen having an atomicweight of less than 33 and z is an integer having a value of more than1, (B) a compound containing at least twoactive hydrogen atoms, each ofsaid active hydrogen atoms being present in a compound selected from thegroup consisting of polyesters, polyhydric alcohol-s, polyhydric phenolsin which the active hydrogen appears in functional groups consisting ofhydroxyl groups, polyamines, polyamides, polycarboxylic acids, water,mixtures thereof and any of the above compounds inwhich at least oneoxygen atom has been replaced by sulfur and (C) a pentanoic acidconsisting essentially of 4,4 bis(4-hydroxyary1)pentanoic acid whereinthe hydroxyaryl radical is a hydroxyphenyl radical and is free fromsubstituents other than alkyl groups of from 1-5 carbon atoms, whereinthe reactive functional groups of (A) and (B)+(C) are present in anequivalent ratio of from about :1 to 1:5 with (B) constituting from 5-65% by weight of (B) (C).

2. The composition of matter of claim 1 wherein the pentanoic acid of(C) consists essentially of 4,4 b1's(4- hydroXyaryDpentanoic acidwherein the hydroxyaryl radical is a hydroxyphenyl radical and is freefrom substituents other than alkyl groups of one carbon atom.

3. The composition of matter of claim 1 wherein the pentanoic acid of(C) is 4,4 bis(4ahydroxyphenyl)pentanoic acid.

4. The composition of matter of claim 3 wherein the reactive functionalgroups of (A) and (B)+(C) are present on an equivalent ratio of fromabout 2:1 to 1:2 with (B) constituting from 565% by weight of (B) v+( 5.The composition of matter as described in claim 4 wherein R of (A) is anorganic aromatic radical.

-6. The composition of matter as described in claim 4 wherein R of (A)is an organic aliphatic radical.

7. A method of preparing a new polymeric composition of matter whichcomprises admixing (A) a compound of the general formula R(NCX) whereinR is an organic radical having a valency equal to z, X is a chalcogenhaving an atomic weight of less than 33 and z is an integer having avalue of more than 1, (B) an organic compound containing at least twoactive hydrogen atoms, each of said active hydrogen atoms being presentin a compound selected from the group consisting of polyesters,polyhydric alcohols in which the active hydrogen appears in functionalgroups consisting of hydroxyl groups, polyhydric phenols, polyamines,polyamides, polycarboxylic acids, water mixtures thereof and any of theabove compounds in which at least one oxygen atom has been replaced bysulfur and (C) a pentanoic acid consisting essentially of 4,4bis(4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is ahydroxyphenyl radical and is free from substituents other than alkylgroups of from 1-5 carbon atoms, wherein the reactive functional groupsof (A) and (B)+(C) are present on an equivalent ratio of from about 5:1to 1:5, with (B) constituting from 565% by weight of (B)+(C), and heatconverting said mixture to an insoluble, infusi'ble resin.

OTHER REFERENCES Bader et aL: J.A.C.S., vol. 76, pages 4, 4 654, 466(September 5, 1954.) (Copy in Scientific Library.)

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.,,230L745 October 6 1959 Sylvan Oa Greenlee It is hereby certified thaterror appears in the printed specification of the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 4 line 21 for "that" read than column 10, TABLE I second columnthereof v last line of Example N00 3 for "and" read an columns 11 and 12TABLE 11, third column thereof, the formula opposite Example No. 2should appear as shown below instead of as in the patent:

OCN NCO columns 15 and 16, 17 and. 1e, and 19 and 20 TABLE Iv secondcolumn thereof for the heading "Diphenolic acid" read I Diphenolic Acid3 same columns 15 to 20 TABLE IV last column thereof in the sun-headingfor "NaCH" read NaOH columns 1'? and 18 TABLE IV-C. 0 third columnthereof and opposite "Ext NO. LXXXIX'Q for "9807" read W 8907 ll columns19 and 20 TABLE IV-D. 9 first column thereof for Ex. NO. "CXXXIX" readCXXIX same columns 19 and 20 TABLE IV--Ea 9 eighth column thereof andopposite "Exo N09 CXLIIIQ for :43" read 73 column 22 line 16,, strikeout polyhydric phenols" and insert the same after "alcohols" in line 14same column 22.,

Signed and sealed this 8th day of November 19609 (SEAL) Attest:

KARL I-I. AXLINE ROBERT Co WATSON Attesting Officer Commissioner ofPatents

1. A COMPOSITION OF MATTER COMPRISING THE POLYMERIC REACTION PRODUCT OF(A) A COMPOUND OF THE GENERAL FORMULA R(NCX)Z9 WHEREIN R IS AN ORGANICRADICAL HAVING A VALENCY EQUAL TO Z, X IS A CHALOGEN HAVING AN ATOMICWEIGHT OF LESS THAN 33 AND Z IS AN INTEGER HAVING A VALUE OF MORE THAN1, (B) A COMPOUND CONTAINING AT LEAST TWO ACTIVE HYDROGEN ATOMS, EACH OFSAID ACTIVE HYDROGEN ATOMS BEING PRESENT IN A COMPOUND SELECTED FROM THEGROUP CONSISTING OF POLYESTERS, POLYHYDRIC ALCOHOLS, POLYHYDRIC PHENOLS,IN WHICH THE ACTIVE HYDROGEN APPEARS IN FUNCTIONAL GROUPS CONSISTING OFHYDROXYL GROUPS, POLYAMINES, POLYAMIDES, POLYCARBOXYLIC ACIDS, WATER,MIXTURES THEREOF AND ANY OF THE ABOVE COMPOUNDS IN WHICH AT LEAST ONEOXYGEN ATOM HAS BEEN REPLACED BY SULFUR AND (C) A PENTANOIC ACIDCONSISTING ESSENTIALLY OF 4,4 BIS(4-HYDROXYARYL)PENTANOIC ACID WHEREINTHE HYDROXYARYL RADICAL IS A HYDROXYPHENYL RADICAL AND IS FREE FROMSUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM 1-5 CARBON ATOMS, WHEREINTHE REACTIVE FUNCITONAL GROUPS OF (A) AND (B)+(C) ARE PRESENT IN ANEQUIVALENT RATIO OF FROM ABOUT 5:1 TO 1:5 WITH (B) CONSTITUTING FROM565% BY WEIGHT OF (B)+(C).